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US10843268B2 - Metal laminated and shaped object, aluminum-based powder for metal laminating and shaping, and method of manufacturing the same - Google Patents

Metal laminated and shaped object, aluminum-based powder for metal laminating and shaping, and method of manufacturing the same Download PDF

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US10843268B2
US10843268B2 US15/545,989 US201615545989A US10843268B2 US 10843268 B2 US10843268 B2 US 10843268B2 US 201615545989 A US201615545989 A US 201615545989A US 10843268 B2 US10843268 B2 US 10843268B2
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powder
lamination
aluminum
metal
equal
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Yoshiki Hashizume
Isao Murakami
Kenji Muramatsu
Kenta ISHIGAMI
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Toyo Aluminum KK
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0408Light metal alloys
    • C22C1/0416Aluminium-based alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/052Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20Direct sintering or melting
    • B22F10/28Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12Both compacting and sintering
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10Processes of additive manufacturing
    • B29C64/141Processes of additive manufacturing using only solid materials
    • B29C64/153Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00Products made by additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/30Process control
    • B22F10/36Process control of energy beam parameters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F12/00Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
    • B22F12/40Radiation means
    • B22F12/41Radiation means characterised by the type, e.g. laser or electron beam
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • B22F2009/0824Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid with a specific atomising fluid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00Aspects linked to processes or compositions used in powder metallurgy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/25Process efficiency

Definitions

  • the present invention relates to metal lamination-shaping.
  • patent literature 1 has disclosed a method of adding a sintering aid to an aluminum powder as needed, and sintering the aluminum powder by heating it in a nitrogen atmosphere containing water vapor at a predetermined partial pressure.
  • Patent literature 1 describes that a sintered object having a high relative density is obtained by using a metal lamination-shaping technique in this method.
  • patent literature 2 has disclosed a method of removing defects by densifying a shaped object by hot isostatic pressing.
  • Patent literature 1 Japanese PCT National Publication No. 2007-521389 (International Publication WO2005/066380)
  • Patent literature 2 Japanese Patent Laid-Open No. 2004-149826
  • the present invention enables to provide a technique of solving the above problems.
  • One aspect of the present invention provides a metal powder used for lamination-shaping which is an aluminum-based powder having a volume-based 50% particle diameter larger than or equal to 10 ⁇ m and smaller than 100 ⁇ m when a particle diameter distribution is measured by a laser diffraction-scattering method, a specific surface area smaller than or equal to 0.5 m 2 /g, and an oxygen amount larger than or equal to 3 mg/m 2 and less than or equal to 10 mg/m 2 per unit surface area,
  • a relationship between a hydrogen amount (X ml in standard state) per 100 g of the aluminum-based powder and a specific surface area (Y m 2 /g), and a relationship between the hydrogen amount (X ml in standard state) and an oxygen amount (Z wt %), are respectively in accordance with following formulas: X/Y ⁇ 151 and, Z/X> 0.0022 preferably, X/Y ⁇ 130 and, Z/X ⁇ 0.003.
  • Another aspect of the present invention provides a method of manufacturing a metal powder used for lamination-shaping, the method comprising:
  • Still another aspect of the present invention provides a metal lamination-shaped object that is lamination-shaped by a three-dimensional lamination-shaping apparatus in a powder bed fusion type using the metal powder as mentioned above,
  • a hydrogen amount is less than or equal to 3 ml per 100 g in standard state, and a relative density is more than or equal to 99%, in the metal lamination-shaped object.
  • a subject of this example embodiment is to examine a defect generating mechanism in metal lamination-shaping using an aluminum-based powder, and control the amounts of hydrogen and oxygen per unit surface area contained in the powder, thereby obtaining a defect-free shaped object without any degassing step.
  • Another subject of this example embodiment is to solve the problem that an aluminum-based powder absorbs moisture with time and the density of a lamination-shaped object decreases.
  • this example embodiment solves the problem that when collecting and reusing a used powder after lamination-shaping, the powder absorbs moisture, so the initial shaped object density cannot be obtained.
  • a method of obtaining an aluminum-based alloy powder of this example embodiment has the following two steps.
  • An aluminum-based alloy powder is manufactured by gas atomization process, more preferably, centrifugal atomization process in an inert gas atmosphere in which the oxygen amount is controlled.
  • the manufactured aluminum-based alloy powder is deaerated in an inert gas at 300° C. to 600° C. and more preferably 400° C. to 500° C., thereby obtaining an aluminum-based alloy powder of this example embodiment.
  • An aluminum-based alloy powder to be used in this example embodiment is an Al—Si—Mg-based alloy.
  • the alloy composition of the aluminum-based alloy powder is not limited to the Al—Si—Mg-based alloy, and it is possible to preferably use a wrought alloy (A1000 series, A2000 series, A3000 series, A4000 series, A5000 series, A6000 series, A7000 series, or A8000 series), a casting alloy, or a diecast alloy.
  • a 900° C. molten metal of the obtained Al-10 wt % St-0.4 wt % Mg alloy is sprayed from a nozzle having a diameter of 2.2 mm, and atomized with 2.5-MPa high-pressure nitrogen.
  • Atomized particles cooled in atmosphere are collected by a cyclone and bag filter.
  • the atomized particles cooled in nitrogen adjusted to have an oxygen amount of 1 ppm or less are collected by the cyclone and bag filter.
  • the atomization conditions and atomization atmosphere are that the atomization pressure was 2.0 to 5.0 MPa, and the atomization atmosphere was nitrogen, argon, or helium.
  • alloy particles having a 50% particle size of 21 ⁇ m are further classified by a centrifugal force classifier, thereby removing most particles having a particle size of 7 ⁇ m or less. Then, particles obtained through a sieve having an opening of 45 ⁇ m (325 meshes) are evenly mixed by using a blender, thereby obtaining an Al-10 wt % Si-0.4 wt % Mg alloy powder of this example embodiment. Note that as this Al-10 wt % Si-0.4 wt % Mg alloy powder, it is also possible to use a powder obtained by collecting particles remaining on the sieve having an opening of 45 ⁇ m (325 meshes). That is, the 50% particle size is desirably 10 ⁇ m (inclusive) to 100 ⁇ m (exclusive).
  • a 1,100° C. molten metal of the obtained Al-10 wt % Si-0.4 wt % Mg alloy is sprayed from a nozzle having a diameter of 1.7 mm onto a graphite rotary disk having a diameter of 100 mm and rotating at 20,000 rpm, which is installed in a nitrogen chamber having a diameter of 4 m and adjusted to have 0.01 wt % of oxygen, thereby obtaining aluminum-based particles.
  • the distance between the spray nozzle and the rotary disk is 15 mm.
  • the obtained aluminum-based particles are collected and further classified by the centrifugal force classifier, thereby removing most particles having a diameter of 7 ⁇ m or less.
  • particles obtained through a sieve having an opening of 45 ⁇ m (325 meshes) are evenly mixed by using a blender, thereby obtaining an Al-10 wt % Si-0.4 wt % Mg alloy powder of this example embodiment.
  • the obtained aluminum-based alloy powder is deaerated in an argon atmosphere as an inert gas at 300° to 600° C. and more preferably 400° C. to 500° C.
  • the heating time is about 10 hours. Note that nitrogen or helium can also be used as the inert gas. Note also that the heating time need only be 1 to 100 hours.
  • the aluminum-based alloy powder of this example embodiment manufactured by gas atomization process or centrifugal atomization process and deaerated in the inert gas atmosphere is used as a metal material for lamination-shaping, thereby shaping a metal lamination-shaped object by a three-dimensional lamination-shaping apparatus in a powder bed fusion type.
  • the aluminum-based alloy powder and its lamination-shaped object were evaluated as follows.
  • the powder of each example or each comparative example was dispersed for 180 sec by an ultrasonic wave, and the dispersion was placed in measurement-system circulating water and measured by using a laser refraction type diffraction particle diameter measurement apparatus (NIKKISO Microtrac MT-3300).
  • the specific surface area was measured by the BET method (MOUNTECH Macsorb HM model-1210).
  • the oxygen amount was measured by the inert gas melting-nondispersive infrared absorption method (HORIBA EMGA-920).
  • Hydrogen amount of powder measured by the Ransley method.
  • Hydrogen amount of lamination-shaped object measured by LECO JAPAN model RHEN602.
  • a scanning electron microscope (JEOL JSM-6510A) was used to fix the powder of each example or each comparative example on a sample table without overlapping particles, and images enlarged by 500 times were electronically photographed in a plurality of fields. After that, at least 100 particles of the same sample were observed, and particles having satellites and particles having no satellites were counted.
  • the fields were photographed such that the number of particles contained in one field was 15 or less.
  • the field size was set such that the longitudinal and lateral sides were 4 to 12 times the 50% particle diameter.
  • the overlapping of particles was minimized, and random extraction was performed, i.e., all vague particles such as apparently fused particles were counted as satellites.
  • Roundness ⁇ c of each of 100 or more particles was measured by image analysis software (KEYENCE VHX-1000) in a plurality of fields photographed in the same manner as in item (3) above, thereby evaluating the average roundness.
  • the Heywood diameter (an equivalent circle diameter) of each of 100 or more particles was calculated by the image analysis software (KEYENCE VHX-1000) in a plurality of fields photographed in the same manner as in item (3) above, and the number of particles smaller than 5 ⁇ m, the number of particles equal to or larger than 5 ⁇ m and smaller than 10 ⁇ m, and the number of particles equal to or larger than 10 ⁇ m were obtained.
  • the abundance of the particles smaller than 5 ⁇ m was calculated by the following equation. If this abundance is 1.0 or less, the fluidity is high.
  • a powder of each example or each comparative example thermally dissolved in a pressure vessel was measured by radio-frequency inductively coupled plasma-atomic emission spectroscopy (Thermo Fisher Scientific iCAP 6500 DUOView).
  • a column having a diameter of 8 mm ⁇ a height of 15 mm was shaped, and the relative density with respect to the true density was measured by the Archimedes method.
  • a column having a diameter of 6 mm ⁇ a length of 38 mm was shaped, and turned into a dumbbell shape having a parallel portion diameter of 3.5 mm and a parallel portion length of 18 mm. Then, a tensile test was conducted by using a universal tester (INSTRON M4206). The crosshead speed was set at 1 mm/min.
  • a metal powder used for lamination-shaping of this example embodiment is an aluminum-based powder having a volume-based 50% particle diameter of 10 ⁇ m (inclusive) to 100 ⁇ m (exclusive) when the particle diameter distribution is measured by the laser diffraction-scattering method, a specific surface area of 0.5 m 2 /g or less, and an oxygen amount of 3 mg/m 2 (inclusive) to 10 mg/m 2 (inclusive) per unit surface area.
  • the relationship between the hydrogen amount (X ml in standard state) per 100 g of the aluminum-based powder and the specific surface area (Y m 2 /g), and the relationship between the hydrogen amount (X ml in standard state) and the oxygen amount (Z wt %), are respectively in accordance with formulas: X/Y ⁇ 151 and Z/X> 0.0022, particularly, X/Y 130 and Z/X 0.003.
  • a metal lamination-shaped object of this example embodiment shaped by a three-dimensional lamination-shaping apparatus in a powder bed fusion type using the above-mentioned metal powder has a hydrogen amount of 3 ml or less (in standard state) per 100 g, and a relative density of 99% or more.
  • the metal powder obtained by the aluminum-based powder of this example embodiment achieves prominent effects as follows.
  • Table 1 shows the manufacture of aluminum-based alloy powders of Examples 1 to 6 according to the present invention and Comparative Examples 1 to 6, lamination-shaped objects using the aluminum-based alloy powders, and the test results of the powders and objects.
  • Example 2 Al—10%Si—0.4%Mg, 51.5 0.18 20.5 0.16 114 0.0078 8.9 ⁇ ⁇ 0.82 1.90 99.5 310 deaerated at 400° C.
  • Example 3 Al—10%So—0.43%Mg, 22.1 0.24 27.7 0.21 115 0.0076 8.8 ⁇ ⁇ 0.82 2.78 99.2 305 deaerated at 425° C.
  • Example 4 Al—10%Si—0.43%Mg, 28.1 0.17 16.7 0.06 98 0.0036 3.5 ⁇ ⁇ 0.93 1.78 99.7 320 centrifugal atomization process
  • Example 5 Al—10%Si—0.43%Mg, 28.1 0.17 10.6 0.09 62 0.0085 5.3 ⁇ ⁇ 0.93 1.23 99.9 326 centrifugal atomization process, deaerated at 400° C.
  • Example 6 Al—10%Si—0.4%Mg, 19.3 0.36 18.3 0.19 51 0.0104 5.3 X X 0.89 1.93 99.1 303 closed circuit, deaerated at 450° C.
  • the obtained 900° C. molten metal was sprayed from a nozzle having a diameter of 2.2 mm, and atomized by 2.5-MPa high-pressure nitrogen. Atomized particles cooled in atmosphere were collected by a cyclone and bag filter. Of the atomized particles collected by the cyclone, alloy particles having a 50% particle diameter of 21 ⁇ m were further classified by a centrifugal force classifier, thereby removing most particles equal to or smaller than 7 ⁇ m.
  • Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • Example 2 A powder of Example 2 was obtained following the same procedures as in Example 1, except that a powder obtained by collecting particles remaining on the sieve having an opening of 45 ⁇ m was used, and the heating temperature in the argon atmosphere was set at 400° C.
  • Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • Example 3 A powder of Example 3 was obtained following the same procedures as in Example 1, except that the heating temperature in the argon atmosphere was set at 425° C.
  • Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • the obtained 1,100° C. molten metal was sprayed from a nozzle having a diameter of 1.7 mm onto a graphite rotary disk having a diameter of 100 mm and rotating at 20,000 rpm, which was installed in a nitrogen chamber having a diameter of 4 m and adjusted to have 0.01 wt % of oxygen, thereby obtaining aluminum-based particles.
  • the distance between the spray nozzle and the rotary disk was 15 mm.
  • the obtained aluminum-based particles were collected and further classified by the centrifugal force classifier, thereby removing most particles equal to or smaller than 7 ⁇ m. Then, particles obtained through a sieve having an opening of 45 ⁇ m (325 meshes) were evenly mixed by using a blender, thereby obtaining an Al-10 wt % Si-0.4 wt % Mg alloy powder of this example.
  • Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • Example 4 The aluminum-based powder obtained in Example 4 was heated in a 450° C. argon atmosphere for 10 hours.
  • Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • the obtained 900° C. molten metal was sprayed from a nozzle having a diameter of 2.2 mm, and atomized by 2.5-MPa high-pressure nitrogen. Atomized particles cooled in nitrogen adjusted to have an oxygen amount of 1 ppm or less were collected by the cyclone and bag filter.
  • alloy particles having a 50% particle diameter of 21 ⁇ m were further classified by the centrifugal force classifier, thereby removing most particles equal to or smaller than 7 ⁇ m. Then, particles obtained through a sieve having an opening of 45 ⁇ m (325 meshes) were evenly mixed by using a blender, thereby obtaining an Al-10 wt % Si-0.4 wt % Mg alloy powder of this example. Furthermore, the obtained alloy powder was heated in an argon atmosphere at 450° C. for 10 hours.
  • Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • An aluminum-based powder of Comparative Example 1 was obtained following the same procedures as in Example 1, except that no heating process in an argon atmosphere was performed.
  • Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • An aluminum-based powder of Comparative Example 2 was obtained following the same procedures as in Example 2, except that no heating process in an argon atmosphere was performed.
  • Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • Table 1 shows the characteristic values of a commercially available, relatively fine aluminum-based powder for metal lamination-shaping, and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • Table 1 shows the characteristic values of a commercially available, relatively coarse aluminum-based powder for metal lamination-shaping, and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • An aluminum-based powder of Comparative Example 5 was obtained following the same procedures as in Example 6, except that no heating process in an argon atmosphere was performed.
  • Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • An aluminum-based powder of Comparative Example 6 was obtained following the same procedures as in Example 1, except that a deaeration process was performed in air at 400° C.
  • Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
  • Example 2 Al—10%Si—0.4%Mg, 20.5 0.16 99.5 22.3 0.17 99.4 21.2 0.16 99.5 deaerated at 400° C.
  • Example 3 Al—10%Si—0.43%Mg, 27.7 0.21 99.2 28.4 0.21 99.2 28.0 0.21 99.2 deaerated at 425° C.
  • Example 4 Al—10%Si—0.43%Mg, 16.7 0.06 99.7 17.1 0.07 99.7 16.9 0.07 99.7 centrifugal atomization process
  • Example 5 Al—10%Si—0.43%Mg, 10.6 0.09 99.9 10.8 0.09 99.9 10.7 0.09 99.9 centrifugal atomization process, deaerated at 400° C.
  • Example 6 Al—10%Si—0.4%Mg, 30.4 0.11 99.1 32.5 0.13 99.0 31.4 0.12 99.1 closed circuit, deaerated at 450° C. Comparative Al—10%Si—0.43%Mg 51.4 0.18 90.1 60.6 0.22 89.9 58.8 0.20 89.9 Example 1 Comparative Al—10%Si—0.4%Mg 40.4 0.18 93.3 47.3 0.20 92.5 45.2 0.19 92.8 Example 2 Comparative Commercially available 26.7 0.06 98.6 51.8 0.41 92.2 36.9 0.35 92.7 Example 3 Al—10%Si—0.4%Mg Comparative Commercially available 28.7 0.16 92.5 32.8 0.20 90.6 31.6 0.22 91.1 Example 4 Al—10%Si—0.4%Mg Comparative Al—10%Si—0.4%Mg Comparative Al—10%Si—0.4%Mg, 60.5 0.17 98.3 77.7 0.45 91.5 87.4 0.37 92.3 Example 5 closed circuit and not de
  • Table 2 shows that the aluminum-based powders of the examples did not largely change the hydrogen amounts and oxygen amounts even after being stored in an open state, and the density of each lamination-shaped object did not decrease even after being aged, collected, and lamination-shaped again. In the comparative examples, however, the density of the lamination-shaped object manufactured from the powder having a Z/X value of less than 0.0022, particularly, less than 0.003 significantly decreased.

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Abstract

The present invention provides a robust metal lamination-shaped object containing aluminum and having no defect. A metal powder used for forming this metal lamination-shaped object is an aluminum-based powder having a volume-based 50% particle diameter larger than or equal to 10 μm and smaller than 100 μm when a particle diameter distribution is measured by a laser diffraction-scattering method, a specific surface area smaller than or equal to 0.5 m2/g, and an oxygen amount larger than or equal to 3 mg/m2 and less than or equal to 10 mg/m2 per unit surface area. A relationship between a hydrogen amount (X ml in standard state) per 100 g of the aluminum-based powder and a specific surface area (Y m2/g), and a relationship between the hydrogen amount (X ml in standard state) and an oxygen amount (Z wt %), are respectively in accordance with formulas: X/Y<151 and Z/X>0.0022. A metal lamination-shaped object, that is lamination-shaped by a three-dimensional lamination-shaping apparatus in a powder bed fusion type using the above metal powder, has a hydrogen amount less than or equal to 3 ml in standard state per 100 g, and a relative density more than or equal to 99%.

Description

RELATED APPLICATION
This application is an application under 35 U.S.C. 371 of International Application No. PCT/JP2016/088773 filed on Dec. 26, 2016, the entire contents of which are incorporated herein by reference.
TECHNICAL FIELD
The present invention relates to metal lamination-shaping.
BACKGROUND ART
In the abovementioned technical field, patent literature 1 has disclosed a method of adding a sintering aid to an aluminum powder as needed, and sintering the aluminum powder by heating it in a nitrogen atmosphere containing water vapor at a predetermined partial pressure. Patent literature 1 describes that a sintered object having a high relative density is obtained by using a metal lamination-shaping technique in this method. Also, patent literature 2 has disclosed a method of removing defects by densifying a shaped object by hot isostatic pressing.
CITATION LIST Patent Literature
Patent literature 1: Japanese PCT National Publication No. 2007-521389 (International Publication WO2005/066380)
Patent literature 2: Japanese Patent Laid-Open No. 2004-149826
SUMMARY OF THE INVENTION Technical Problem
Unfortunately, it is difficult for the technique described in abovementioned cited literature 1 to completely remove defects, and there is also a problem that the relative density of a sintered object largely decreases even when the vapor partial pressure has slightly changed. In addition, the method described in abovementioned cited reference 2 is very difficult to put to practical use because the process is complicated and the cost is high.
The present invention enables to provide a technique of solving the above problems.
Solution to Problem
One aspect of the present invention provides a metal powder used for lamination-shaping which is an aluminum-based powder having a volume-based 50% particle diameter larger than or equal to 10 μm and smaller than 100 μm when a particle diameter distribution is measured by a laser diffraction-scattering method, a specific surface area smaller than or equal to 0.5 m2/g, and an oxygen amount larger than or equal to 3 mg/m2 and less than or equal to 10 mg/m2 per unit surface area,
wherein a relationship between a hydrogen amount (X ml in standard state) per 100 g of the aluminum-based powder and a specific surface area (Y m2/g), and a relationship between the hydrogen amount (X ml in standard state) and an oxygen amount (Z wt %), are respectively in accordance with following formulas:
X/Y<151 and,
Z/X>0.0022
preferably,
X/Y≤130 and,
Z/X≥0.003.
Another aspect of the present invention provides a method of manufacturing a metal powder used for lamination-shaping, the method comprising:
manufacturing an aluminum-based alloy powder by gas atomization process or centrifugal atomization process in an inert gas atmosphere in which an oxygen amount is controlled; and
deaerating the aluminum-based alloy powder in an inert gas at 300° C. to 600° C.
Still another aspect of the present invention provides a metal lamination-shaped object that is lamination-shaped by a three-dimensional lamination-shaping apparatus in a powder bed fusion type using the metal powder as mentioned above,
wherein a hydrogen amount is less than or equal to 3 ml per 100 g in standard state, and a relative density is more than or equal to 99%, in the metal lamination-shaped object.
Advantageous Effects of Invention
According to the present invention, a robust metal lamination-shaped object containing aluminum and having no defect can be obtained.
DESCRIPTION OF EXAMPLE EMBODIMENTS
Example embodiments of the present invention will now be described in detail with reference to the drawings. It should be noted that constituent elements described in the following example embodiments are merely examples, and do not intend to limit the technical scope of the present invention to them. Note also that in this specification, “a standard state” is a state at 0° C. and 1 atm.
<Technical Premise>
In casting or powder metallurgy using an aluminum-based material, it is known that hydrogen contained in the aluminum-based material causes a defect. When manufacturing an aluminum alloy by casting or powder metallurgy, therefore, a method of removing solute hydrogen or surface hydrogen (water or the like) by performing degassing during the process is generally performed. However, a degassing step like this is very difficult to perform when using an aluminum-based material in metal lamination-shaping. Even if the degassing step can be performed, degassing requires a very long time and significantly decreases the productivity.
(Problems)
A subject of this example embodiment is to examine a defect generating mechanism in metal lamination-shaping using an aluminum-based powder, and control the amounts of hydrogen and oxygen per unit surface area contained in the powder, thereby obtaining a defect-free shaped object without any degassing step.
Another subject of this example embodiment is to solve the problem that an aluminum-based powder absorbs moisture with time and the density of a lamination-shaped object decreases. For example, this example embodiment solves the problem that when collecting and reusing a used powder after lamination-shaping, the powder absorbs moisture, so the initial shaped object density cannot be obtained.
<Aluminum-Based Alloy Powder>
A method of obtaining an aluminum-based alloy powder of this example embodiment has the following two steps.
(1) An aluminum-based alloy powder is manufactured by gas atomization process, more preferably, centrifugal atomization process in an inert gas atmosphere in which the oxygen amount is controlled.
(2) Then, the manufactured aluminum-based alloy powder is deaerated in an inert gas at 300° C. to 600° C. and more preferably 400° C. to 500° C., thereby obtaining an aluminum-based alloy powder of this example embodiment.
(1: Manufacture of Aluminum-Based Alloy Powder)
An aluminum-based alloy powder to be used in this example embodiment is an Al—Si—Mg-based alloy. In particular, Si=10 wt % and Mg=0.4 wt % are added to an Al ground metal having a purity of 99.7 wt %, and heated Al-10 wt % Si-0.4 wt % Mg is used as an alloy molten metal. Note that the alloy composition of the aluminum-based alloy powder is not limited to the Al—Si—Mg-based alloy, and it is possible to preferably use a wrought alloy (A1000 series, A2000 series, A3000 series, A4000 series, A5000 series, A6000 series, A7000 series, or A8000 series), a casting alloy, or a diecast alloy.
(Use of Gas Atomization Process)
A 900° C. molten metal of the obtained Al-10 wt % St-0.4 wt % Mg alloy is sprayed from a nozzle having a diameter of 2.2 mm, and atomized with 2.5-MPa high-pressure nitrogen. Atomized particles cooled in atmosphere are collected by a cyclone and bag filter. In addition, the atomized particles cooled in nitrogen adjusted to have an oxygen amount of 1 ppm or less are collected by the cyclone and bag filter. The atomization conditions and atomization atmosphere are that the atomization pressure was 2.0 to 5.0 MPa, and the atomization atmosphere was nitrogen, argon, or helium.
Of the atomized particles collected by the cyclone, alloy particles having a 50% particle size of 21 μm are further classified by a centrifugal force classifier, thereby removing most particles having a particle size of 7 μm or less. Then, particles obtained through a sieve having an opening of 45 μm (325 meshes) are evenly mixed by using a blender, thereby obtaining an Al-10 wt % Si-0.4 wt % Mg alloy powder of this example embodiment. Note that as this Al-10 wt % Si-0.4 wt % Mg alloy powder, it is also possible to use a powder obtained by collecting particles remaining on the sieve having an opening of 45 μm (325 meshes). That is, the 50% particle size is desirably 10 μm (inclusive) to 100 μm (exclusive).
(Use of Centrifugal Atomization Process)
A 1,100° C. molten metal of the obtained Al-10 wt % Si-0.4 wt % Mg alloy is sprayed from a nozzle having a diameter of 1.7 mm onto a graphite rotary disk having a diameter of 100 mm and rotating at 20,000 rpm, which is installed in a nitrogen chamber having a diameter of 4 m and adjusted to have 0.01 wt % of oxygen, thereby obtaining aluminum-based particles. The distance between the spray nozzle and the rotary disk is 15 mm. The obtained aluminum-based particles are collected and further classified by the centrifugal force classifier, thereby removing most particles having a diameter of 7 μm or less. Then, particles obtained through a sieve having an opening of 45 μm (325 meshes) are evenly mixed by using a blender, thereby obtaining an Al-10 wt % Si-0.4 wt % Mg alloy powder of this example embodiment.
(2: Deaeration of Aluminum-Based Alloy Powder)
The obtained aluminum-based alloy powder is deaerated in an argon atmosphere as an inert gas at 300° to 600° C. and more preferably 400° C. to 500° C. The heating time is about 10 hours. Note that nitrogen or helium can also be used as the inert gas. Note also that the heating time need only be 1 to 100 hours.
<Metal Lamination-Shaped Object>
The aluminum-based alloy powder of this example embodiment manufactured by gas atomization process or centrifugal atomization process and deaerated in the inert gas atmosphere is used as a metal material for lamination-shaping, thereby shaping a metal lamination-shaped object by a three-dimensional lamination-shaping apparatus in a powder bed fusion type.
Note that an example using EOS EOSINT M280 including a 400-W output class Yb fiber laser (beam spot diameter=0.1 mm) as the three-dimensional lamination-shaping apparatus will be described below, but the feature of the metal lamination-shaped object of this example embodiment is not limited by the lamination-shaping method.
<Evaluation Methods>
The aluminum-based alloy powder and its lamination-shaped object were evaluated as follows.
(1) Particle Diameter Distribution Measurement
The powder of each example or each comparative example was dispersed for 180 sec by an ultrasonic wave, and the dispersion was placed in measurement-system circulating water and measured by using a laser refraction type diffraction particle diameter measurement apparatus (NIKKISO Microtrac MT-3300).
(2) Measurement of Specific Surface Area
The specific surface area was measured by the BET method (MOUNTECH Macsorb HM model-1210).
(3) Measurement of Oxygen Amount
The oxygen amount was measured by the inert gas melting-nondispersive infrared absorption method (HORIBA EMGA-920).
(4) Measurement of Hydrogen Amount
Hydrogen amount of powder: measured by the Ransley method.
Hydrogen amount of lamination-shaped object: measured by LECO JAPAN model RHEN602.
(3) Calculation of Ratio of Particles Having Satellites
A scanning electron microscope (JEOL JSM-6510A) was used to fix the powder of each example or each comparative example on a sample table without overlapping particles, and images enlarged by 500 times were electronically photographed in a plurality of fields. After that, at least 100 particles of the same sample were observed, and particles having satellites and particles having no satellites were counted.
The fields were photographed such that the number of particles contained in one field was 15 or less. The field size was set such that the longitudinal and lateral sides were 4 to 12 times the 50% particle diameter. The overlapping of particles was minimized, and random extraction was performed, i.e., all vague particles such as apparently fused particles were counted as satellites.
(4) Roundness
Roundness ψc of each of 100 or more particles was measured by image analysis software (KEYENCE VHX-1000) in a plurality of fields photographed in the same manner as in item (3) above, thereby evaluating the average roundness.
(5) Calculation and Evaluation of Abundance of Particles Smaller Than 5 μm
The Heywood diameter (an equivalent circle diameter) of each of 100 or more particles was calculated by the image analysis software (KEYENCE VHX-1000) in a plurality of fields photographed in the same manner as in item (3) above, and the number of particles smaller than 5 μm, the number of particles equal to or larger than 5 μm and smaller than 10 μm, and the number of particles equal to or larger than 10 μm were obtained. The abundance of the particles smaller than 5 μm was calculated by the following equation. If this abundance is 1.0 or less, the fluidity is high.
Evaluation of Fluidity:
(The number of particles having diameters smaller than 5 μm×3)/(the number of particles having diameters of 10 μm or more)
(6) Measurement of Alloy Composition
A powder of each example or each comparative example thermally dissolved in a pressure vessel was measured by radio-frequency inductively coupled plasma-atomic emission spectroscopy (Thermo Fisher Scientific iCAP 6500 DUOView).
(7) Characteristics of Shaped Object
Shaping was performed by EOS EOSINT M280 including a 400-W output class Yb fiber laser (beam spot diameter=0.1 mm).
A column having a diameter of 8 mm×a height of 15 mm was shaped, and the relative density with respect to the true density was measured by the Archimedes method.
Also, a column having a diameter of 6 mm×a length of 38 mm was shaped, and turned into a dumbbell shape having a parallel portion diameter of 3.5 mm and a parallel portion length of 18 mm. Then, a tensile test was conducted by using a universal tester (INSTRON M4206). The crosshead speed was set at 1 mm/min.
<Evaluation Results>
(Metal Powder Used for Lamination-Shaping)
A metal powder used for lamination-shaping of this example embodiment is an aluminum-based powder having a volume-based 50% particle diameter of 10 μm (inclusive) to 100 μm (exclusive) when the particle diameter distribution is measured by the laser diffraction-scattering method, a specific surface area of 0.5 m2/g or less, and an oxygen amount of 3 mg/m2 (inclusive) to 10 mg/m2 (inclusive) per unit surface area.
Also, in the metal powder used for lamination-shaping of this example embodiment, the relationship between the hydrogen amount (X ml in standard state) per 100 g of the aluminum-based powder and the specific surface area (Y m2/g), and the relationship between the hydrogen amount (X ml in standard state) and the oxygen amount (Z wt %), are respectively in accordance with formulas:
X/Y<151 and Z/X>0.0022, particularly, X/Y130 and Z/X0.003.
(Metal Lamination-Shaped Object)
A metal lamination-shaped object of this example embodiment shaped by a three-dimensional lamination-shaping apparatus in a powder bed fusion type using the above-mentioned metal powder has a hydrogen amount of 3 ml or less (in standard state) per 100 g, and a relative density of 99% or more.
Effects of This Example Embodiment
The metal powder obtained by the aluminum-based powder of this example embodiment achieves prominent effects as follows.
  • (1) A defect-free robust metal lamination-shaped object which is difficult to manufacture by the conventional aluminum-based alloy powder is obtained.
  • (2) The fluidity and spreadability which cannot be obtained by a well-known aluminum-based alloy powder are achieved. In the lamination-shaping step, therefore, a uniform powder bed is formed, and a dense shaped object is obtained.
  • (3) The conventional aluminum-based powder has the problem that the oxygen amount and/or the hydrogen amount increases, and the density of the lamination-shaped object decreases. However, the metal powder used for lamination-shaping of this example embodiment is stable, and a high-density lamination-shaped object is obtained even when collecting and reusing the powder.
EXAMPLES
Table 1 shows the manufacture of aluminum-based alloy powders of Examples 1 to 6 according to the present invention and Comparative Examples 1 to 6, lamination-shaped objects using the aluminum-based alloy powders, and the test results of the powders and objects.
TABLE 1
Characteristics of Aluminum-Based Alloy Powders and Characteristics of 3D Lamination-shaped Objects using Powders
Powder Shaped
hydro- object
Powder gen hydro-
specific amount Powder Oxygen gen Shaped Shaped
surface X oxygen amount amount object object
Powder area [cc/ amount per unit SEM image [cc/ relative tensile
Composition of D50 Y 100 g Z area analysis results 100 g density strength
aluminum alloy [μm] [m2/g] Al] [%] X/Y Z/X (mg/m2) {circle around (1)} {circle around (2)} {circle around (3)} Al] (%) [Mpa]
Example 1 Al—10%Si—0.4%Mg, 22.1 0.24 23.8 0.21 99 0.0088 8.8 0.82 2.04 99.7 316
deaerated at 450° C.
Example 2 Al—10%Si—0.4%Mg, 51.5 0.18 20.5 0.16 114 0.0078 8.9 0.82 1.90 99.5 310
deaerated at 400° C.
Example 3 Al—10%So—0.43%Mg, 22.1 0.24 27.7 0.21 115 0.0076 8.8 0.82 2.78 99.2 305
deaerated at 425° C.
Example 4 Al—10%Si—0.43%Mg, 28.1 0.17 16.7 0.06 98 0.0036 3.5 0.93 1.78 99.7 320
centrifugal atomization
process
Example 5 Al—10%Si—0.43%Mg, 28.1 0.17 10.6 0.09 62 0.0085 5.3 0.93 1.23 99.9 326
centrifugal atomization
process, deaerated at
400° C.
Example 6 Al—10%Si—0.4%Mg, 19.3 0.36 18.3 0.19 51 0.0104 5.3 X X 0.89 1.93 99.1 303
closed circuit, deaerated
at 450° C.
Compar- Al—10%Si—0.43%Mg 22.1 0.24 51.4 0.18 214 0.0035 7.5 0.82 4.82 90.1 290
ative
Example 1
Compar- Al—10%Si—0.4%Mg 51.5 0.18 40.4 0.18 224 0.0045 10.0 0.82 3.74 93.3 293
ative
Example 2
Compar- Commercially available 29.0 0.24 26.7 0.06 111 0.0022 2.5 X X 0.90 1.70 98.6 297
ative Al—10%Si—0.4%Mg
Example 3
Compar- Commercially available 45.5 0.19 28.7 0.16 151 0.0056 8.4 0.68 3.00 92.5 280
ative Al—10%Si—0.4%Mg
Example 4
Compar- Al—10%Si—0.4%Mg, 19.1 0.34 60.5 0.17 178 0.0028 5.0 X X 0.88 4.11 98.3 285
ative closed circuit and
Example 5 not deaerated
Compar- Al—10%Si—0.4%Mg, 22.3 0.22 28.5 0.33 130 0.0116 15.0 0.83 2.1 93.5 275
ative deaerated at 400° C.
Example 6 in air
SEM image analysis results
{circle around (1)} ◯: when the number of particles having diameters of 5 μm or less × 3 ≤ the number of particles having diameters of 10 μm or more,
X: in other cases
{circle around (2)} ◯: when the number of particles having satellites ≤ the number of particles having no satellites,
X: in other cases
{circle around (3)} Average roundness
<Aluminum-Based Alloy Powders of Examples 1 to 6 and Lamination-Shaped Objects Thereof>
The manufacture of aluminum-based alloy powders of Examples 1 to 6, lamination-shaped objects using the powders, and the test results of the powders and objects will be explained below.
Example 1
Si=10 wt % and Mg=0.4 wt % were added to an Al ground metal having a purity of 99.7 wt %, and an Al-10 wt % Si-0.4 wt % Mg alloy molten metal was formed by heating the obtained material. The obtained 900° C. molten metal was sprayed from a nozzle having a diameter of 2.2 mm, and atomized by 2.5-MPa high-pressure nitrogen. Atomized particles cooled in atmosphere were collected by a cyclone and bag filter. Of the atomized particles collected by the cyclone, alloy particles having a 50% particle diameter of 21 μm were further classified by a centrifugal force classifier, thereby removing most particles equal to or smaller than 7 μm. Then, particles obtained through a sieve having an opening of 45 μm (325 meshes) were evenly mixed by using a blender, thereby, obtaining an Al-10 wt % Si-0.4 wt % Mg alloy powder of this example. Furthermore, the obtained alloy powder was heated in an argon atmosphere at 450° C. for 10 hours.
Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
Example 2
A powder of Example 2 was obtained following the same procedures as in Example 1, except that a powder obtained by collecting particles remaining on the sieve having an opening of 45 μm was used, and the heating temperature in the argon atmosphere was set at 400° C.
Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
Example 3
A powder of Example 3 was obtained following the same procedures as in Example 1, except that the heating temperature in the argon atmosphere was set at 425° C.
Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
Example 4
Si=10 wt % and Mg=0.4 wt % were added to an Al ground metal having a purity of 99.7 wt %, and an Al-10 wt % Si-0.4 wt % Mg alloy molten metal was formed by heating the obtained material. The obtained 1,100° C. molten metal was sprayed from a nozzle having a diameter of 1.7 mm onto a graphite rotary disk having a diameter of 100 mm and rotating at 20,000 rpm, which was installed in a nitrogen chamber having a diameter of 4 m and adjusted to have 0.01 wt % of oxygen, thereby obtaining aluminum-based particles. The distance between the spray nozzle and the rotary disk was 15 mm. The obtained aluminum-based particles were collected and further classified by the centrifugal force classifier, thereby removing most particles equal to or smaller than 7 μm. Then, particles obtained through a sieve having an opening of 45 μm (325 meshes) were evenly mixed by using a blender, thereby obtaining an Al-10 wt % Si-0.4 wt % Mg alloy powder of this example.
Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
Example 5
The aluminum-based powder obtained in Example 4 was heated in a 450° C. argon atmosphere for 10 hours.
Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
Example 6
Si=10 wt % and Mg=0.4 wt % were added to an Al ground metal having a purity of 99.7 wt %, and an Al-10 wt % Si-0.4 wt % Mg alloy molten metal was formed by heating the obtained material. The obtained 900° C. molten metal was sprayed from a nozzle having a diameter of 2.2 mm, and atomized by 2.5-MPa high-pressure nitrogen. Atomized particles cooled in nitrogen adjusted to have an oxygen amount of 1 ppm or less were collected by the cyclone and bag filter. Of the atomized particles collected by the cyclone, alloy particles having a 50% particle diameter of 21 μm were further classified by the centrifugal force classifier, thereby removing most particles equal to or smaller than 7 μm. Then, particles obtained through a sieve having an opening of 45 μm (325 meshes) were evenly mixed by using a blender, thereby obtaining an Al-10 wt % Si-0.4 wt % Mg alloy powder of this example. Furthermore, the obtained alloy powder was heated in an argon atmosphere at 450° C. for 10 hours.
Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
<Aluminum-Based Alloy Powders of Comparative Examples 1 to 6 and Lamination-Shaped Objects Thereof>
For comparison with the manufacture of the aluminum-based alloy powders of Examples 1 to 6 and the lamination-shaped objects using the powders, aluminum-based alloy powders of Comparative Examples 1 to 6, lamination-shaped objects using the powders, and the test results of the powders and objects will be explained below.
Comparative Example 1
An aluminum-based powder of Comparative Example 1 was obtained following the same procedures as in Example 1, except that no heating process in an argon atmosphere was performed.
Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
Comparative Example 2
An aluminum-based powder of Comparative Example 2 was obtained following the same procedures as in Example 2, except that no heating process in an argon atmosphere was performed.
Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
Comparative Example 3
Table 1 shows the characteristic values of a commercially available, relatively fine aluminum-based powder for metal lamination-shaping, and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
Comparative Example 4
Table 1 shows the characteristic values of a commercially available, relatively coarse aluminum-based powder for metal lamination-shaping, and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
Comparative Example 5
An aluminum-based powder of Comparative Example 5 was obtained following the same procedures as in Example 6, except that no heating process in an argon atmosphere was performed.
Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
Comparative Example 6
An aluminum-based powder of Comparative Example 6 was obtained following the same procedures as in Example 1, except that a deaeration process was performed in air at 400° C.
Table 1 shows the characteristic values of this powder and the relative density and tensile strength of a lamination-shaped object manufactured by using the powder.
<Verification of Stability and Reuse>
The aluminum-based alloy powders of Examples 1 to 5 and Comparative Examples 1 to 6 described above were stored in an open state at room temperature for one month, and repetitively lamination-shaped five times. After that, the hydrogen amounts and oxygen amounts of the collected powders were measured. Table 2 shows the obtained results.
TABLE 2
Changes in Hydrogen Amounts and Oxygen Amounts of Aluminum Alloy Powders and Lamination-shaped Object Densities
Immediately after manufacture (unsealing)
Powder Powder Shaped object
hydrogen oxygen relative After storage at room Collected after lamination-
Aluminum alloy amount amount density temperature for 1 month shaping (5 times)
composition [cc/100 gAl] [%] (%) [cc/100 gAl] [%] (%) (cc/100 gAl] [%] (%)
Example 1 Al—10%Si—0.4%Mg, 23.8 0.21 99.7 24.1 0.22 99.6 23.9 0.21 99.6
deaerated at 450° C.
Example 2 Al—10%Si—0.4%Mg, 20.5 0.16 99.5 22.3 0.17 99.4 21.2 0.16 99.5
deaerated at 400° C.
Example 3 Al—10%Si—0.43%Mg, 27.7 0.21 99.2 28.4 0.21 99.2 28.0 0.21 99.2
deaerated at 425° C.
Example 4 Al—10%Si—0.43%Mg, 16.7 0.06 99.7 17.1 0.07 99.7 16.9 0.07 99.7
centrifugal atomization
process
Example 5 Al—10%Si—0.43%Mg, 10.6 0.09 99.9 10.8 0.09 99.9 10.7 0.09 99.9
centrifugal atomization
process, deaerated at
400° C.
Example 6 Al—10%Si—0.4%Mg, 30.4 0.11 99.1 32.5 0.13 99.0 31.4 0.12 99.1
closed circuit, deaerated
at 450° C.
Comparative Al—10%Si—0.43%Mg 51.4 0.18 90.1 60.6 0.22 89.9 58.8 0.20 89.9
Example 1
Comparative Al—10%Si—0.4%Mg 40.4 0.18 93.3 47.3 0.20 92.5 45.2 0.19 92.8
Example 2
Comparative Commercially available 26.7 0.06 98.6 51.8 0.41 92.2 36.9 0.35 92.7
Example 3 Al—10%Si—0.4%Mg
Comparative Commercially available 28.7 0.16 92.5 32.8 0.20 90.6 31.6 0.22 91.1
Example 4 Al—10%Si—0.4%Mg
Comparative Al—10%Si—0.4%Mg, 60.5 0.17 98.3 77.7 0.45 91.5 87.4 0.37 92.3
Example 5 closed circuit and
not deaerated
Comparative Al—10%Si—0.4%Mg, 28.5 0.33 93.5 29.4 0.34 93.3 29.1 0.33 93.4
Example 6 deaerated in air at
400° C.

Aging Stability Test
Stored at room temperature for 1 month: average temperature=25° C., average relative humidity=60%
Collected after lamination-shaping: lamination-shaping→collection→pulverization→sieving were repeated 5 times
Table 2 shows that the aluminum-based powders of the examples did not largely change the hydrogen amounts and oxygen amounts even after being stored in an open state, and the density of each lamination-shaped object did not decrease even after being aged, collected, and lamination-shaped again. In the comparative examples, however, the density of the lamination-shaped object manufactured from the powder having a Z/X value of less than 0.0022, particularly, less than 0.003 significantly decreased.

Claims (10)

The invention claimed is:
1. A metal powder used for lamination-shaping which is an aluminum-based powder having a volume-based 50% particle diameter larger than or equal to 10 μm and smaller than 100 μm when a particle diameter distribution is measured by a laser diffraction-scattering method, a specific surface area smaller than or equal to 0.5 m2/g, and an oxygen amount larger than or equal to 3.0 mg/m2 and less than or equal to 10.0 mg/m2 per unit surface area,
wherein a relationship between a hydrogen amount (X ml in standard state) per 100 g of the aluminum-based powder and a specific surface area (Y m2/g), and a relationship between the hydrogen amount (X ml in standard state) and an oxygen amount (Z wt %), are respectively in accordance with following formulas:

X/Y<151 and,

Z/X>0.0022.
2. The metal powder according to claim 1, wherein the relationship between the hydrogen amount (X ml in standard state) and the specific surface area (Y m2/g), and the relationship between the hydrogen amount (X ml in standard state) and the oxygen amount (Z wt %), are respectively in accordance with following formulas:

X/Y≤130 and,

Z/X≥0.003.
3. A method of manufacturing the metal powder of claim 1 used for lamination-shaping, the method comprising:
manufacturing an aluminum-based alloy powder by gas atomization process or centrifugal atomization process in an inert gas atmosphere in which an oxygen amount is controlled; and
deaerating the aluminum-based alloy powder in an inert gas at 300° C. to 600° C.
4. The method according to claim 3, wherein, in said deaerating step, the aluminum-based alloy powder is deaerated in an inert gas at 400° C. to 500° C.
5. The method according to claim 3, wherein, in said deaerating step, the aluminum-based alloy powder is deaerated in an inert gas for 1 to 100 hours.
6. A metal lamination-shaped object that is lamination-shaped by a three-dimensional lamination-shaping apparatus in a powder bed fusion type using the metal powder according to claim 1,
wherein a hydrogen amount is less than or equal to 3 ml per 100 g in standard state, and a relative density is more than or equal to 99%, in the metal lamination-shaped object.
7. A metal lamination-shaped object that is lamination-shaped by a three-dimensional lamination-shaping apparatus in a powder bed fusion type using the metal powder according to claim 2,
wherein a hydrogen amount is less than or equal to 3 ml per 100 g in standard state, and a relative density is more than or equal to 99%, in the metal lamination-shaped object.
8. The method according to claim 4, wherein, in said deaerating step, the aluminum-based alloy powder is deaerated in an inert gas for 1 to 100 hours.
9. The method according to claim 5, where the deaerating step is performed for 10 hours.
10. The method according to claim 8, where the deaerating step is performed for 10 hours.
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